Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/097—Plasticisers; Charge controlling agents

Definitions

• the present invention relates to a method for producing an electrostatic charge image developing toner used for developing a latent image formed in an electrophotography method, an electrostatic recording method, an electrostatic printing method, or the like.
• Patent Document 1 describes a toner containing an amorphous polyester resin, a binder resin containing a crystalline polyester resin, and a release agent, wherein the amorphous polyester resin is terephthalate.
• An amorphous polyester resin obtained by polycondensation of a dicarboxylic acid monomer containing an acid or isophthalic acid as a main component and a diol monomer containing ethylene glycol as a main component, wherein the crystalline polyester resin has 9 to 9 carbon atoms.
• JP 2018-59964 A discloses an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom having 3 to 5 carbon atoms, and an aromatic dicarboxylic acid compound.
• An amorphous polyester A which is a polycondensate with a carboxylic acid component
• a crystalline polyester C which is a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid-based compound.
• a pulverized toner obtained by a melt-kneading method wherein the amorphous polyester A has a glass transition temperature within a specific range, and the solubility parameter of the amorphous polyester A and the solubility parameter and crystallization temperature of the crystalline polyester C are A pulverized toner that satisfies a specific relationship is described, and the toner is described to be excellent in low-temperature fixability, heat-resistant storage stability, and suppression of blurring.
• Patent Document 3 discloses a polycondensation product of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom, a carboxylic acid component, and polyethylene terephthalate, which is a polyester resin.
• A and a crystalline resin containing a polyester resin C which is a polycondensation product of an alcohol component and a carboxylic acid component containing 50 mol% or more and 100 mol% or less of ethylene glycol, and is amorphous
• a toner for developing an electrostatic charge image containing a binder resin composition for toner in which the mass ratio of a resin to a crystalline resin is within a specific range is disclosed, and the toner for developing an electrostatic charge image has low-temperature fixability and low-temperature fixability. It is described that the fixing property is stable over time and excellent in durability.
• the present invention is a method for producing a toner for electrostatic charge image development, comprising the steps of aggregating and fusing resin particles containing an amorphous resin and a crystalline resin in the same or different particles in an aqueous medium.
• the amorphous resin contains an amorphous polyester resin (A) which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b),
• the crystalline resin contains a crystalline polyester resin (C) which is a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d).
• the present invention relates to a method for producing a toner for electrostatic charge image development.
• the present invention relates to a method for producing an electrostatic charge image developing toner having excellent low-temperature fixability and a narrow charge amount distribution.
• the present inventors discovered an amorphous polyester resin (A) containing an amorphous polyester resin (A) which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b). and a crystalline resin containing a crystalline polyester resin (C) which is a polycondensation product of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d), in the same or different particles.
• a toner for electrostatic charge image development produced by a method including a step of aggregating particles in an aqueous medium and a step of fusing particles is excellent in low-temperature fixability and has a narrow charge amount distribution. That is, the present invention relates to the following [1].
• a method for producing a toner for electrostatic charge image development comprising a step of aggregating and fusing resin particles containing an amorphous resin and a crystalline resin in the same or different particles in an aqueous medium, ,
• the amorphous resin contains an amorphous polyester resin (A) which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b),
• the crystalline resin contains a crystalline polyester resin (C) which is a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d).
• an electrostatic charge image developing toner which is excellent in low-temperature fixability and has a narrow charge amount distribution.
• a method for producing a toner for developing an electrostatic charge image (hereinafter also simply referred to as "toner”) of the present invention comprises aggregating resin particles containing an amorphous resin and a crystalline resin in the same or different particles in an aqueous medium. and fusing.
• the amorphous resin is an amorphous polyester resin (A) (hereinafter simply referred to as Also referred to as “resin (A)").
• the crystalline resin is a crystalline polyester resin (C) that is a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d) (hereinafter also simply referred to as "resin (C)"). ).
• resin (C) a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d) (hereinafter also simply referred to as "resin (C)").
• the detailed mechanism by which a toner having excellent low-temperature fixability and a narrow charge amount distribution can be obtained by the production method of the present invention is not clear, it is considered as follows.
• the hydrophobic crystalline polyester resin among the binder resins exists in large amounts inside the toner by avoiding the interface with water during production. , is disadvantageous for rapid thermal response during fixing.
• the production method of the present invention by using a crystalline resin containing a crystalline polyester resin (C) in which the alcohol component (c) contains ethylene glycol and whose hydrophilicity is relatively improved, the toner surface is The resin (C) can be present in the vicinity of the .
• the thermal responsiveness of the toner is improved, the toner can be melted by instant heating at the time of fixing, and the toner can be produced with excellent low-temperature fixability at high speed.
• an amorphous polyester resin (A) which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b)
• an amorphous polyester resin (A) which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b)
• an amorphous The hydrophilicity of the resin is also improved, and in the step of aggregating the resin particles, an amorphous resin containing an amorphous polyester resin (A) having higher hydrophilicity than the resin (C) is formed on the outermost surface of the agglomerated particles.
• the surface exposure of the resin (C) is suppressed, so that a toner with a narrow charge amount distribution is obtained, and the chargeability of the toner is considered to be improved. be done.
• This effect is not limited to the case where the amorphous resin containing the resin (A) and the crystalline resin containing the resin (C) are contained in different resin particles, and the amorphous resin containing the resin (A) and the resin It is considered that a similar result can be obtained even when the crystalline resin containing (C) is contained in the same resin particles.
• the carboxylic acid component of the polyester resin includes not only the compound but also an anhydride that decomposes during the reaction to generate a carboxylic acid, and an alkyl ester of each carboxylic acid (an alkyl group having 1 to 3 carbon atoms below) are also included.
• an alkyl ester of each carboxylic acid an alkyl group having 1 to 3 carbon atoms below
• Whether a resin is crystalline or amorphous is determined by the crystallinity index.
• the crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C)/maximum endothermic peak temperature (°C)) in the measurement method described in the Examples below.
• a crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less.
• Amorphous resins are those in which no endothermic peak is observed or, if observed, the crystallinity index is less than 0.6 or greater than 1.4.
• the crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate.
• references to parentheses “(iso or tertiary)" and “(iso)” mean both the presence and absence of these prefixes, and the absence of these prefixes. In some cases, the normal is shown.
• “(Meth)acrylic acid” means at least one selected from acrylic acid and methacrylic acid.
• (Meth)acrylate means at least one selected from acrylate and methacrylate.
• a "(meth)acryloyl group” means at least one selected from an acryloyl group and a methacryloyl group.
• Styrenic compound means unsubstituted or substituted styrene.
• backbone is meant the longest relatively connecting chain in the addition polymer.
• a method for producing a toner according to an embodiment of the present invention includes a step of aggregating and fusing resin particles containing an amorphous resin and a crystalline resin in the same or different particles in an aqueous medium.
• Resin particles can be obtained, for example, by a phase inversion emulsification method using an amorphous resin and/or a crystalline resin, as described later.
• the present invention will be described below by taking the embodiment as an example.
• aggregated particles 1 are obtained by aggregating the resin particles containing the same or different particles of the amorphous resin and the crystalline resin in the aqueous medium.
• the resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion are each an aqueous dispersion of resin particles, an aqueous dispersion of colorant particles, and an aqueous dispersion of release agent particles. preferable.
• the amorphous resin is used as a binder resin for toner, and is an amorphous polyester which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b). It contains resin (A). Resin (A) has higher hydrophilicity than crystalline polyester resin (C). Therefore, it is considered that the amorphous resin exists on the outermost surface of the toner obtained by the production method of the present invention, and the surface exposure of the resin (C) is suppressed.
• the polyester resin (A) is a polycondensate of the alcohol component (a) and the carboxylic acid component (b), and the alcohol component contains an aliphatic diol having 2 to 5 carbon atoms.
• Aliphatic diols having 2 to 5 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol.
• 2,3-butanediol 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3 -pentanediol, 2,4-pentanediol, neopentyl glycol and the like.
• Aliphatic diols having 2 to 5 carbon atoms are preferably ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1 ,3-propanediol and neopentyl glycol, more preferably ethylene glycol, 1,2-propanediol, 2,3-butanediol and neopentyl glycol.
• the content of the aliphatic diol having 2 to 5 carbon atoms is preferably 85 mol% or more, more preferably 90 mol, from the viewpoint of suppressing the surface exposure of the crystalline polyester resin (C). % or more, more preferably 95 mol % or more, and 100 mol % or less, preferably 100 mol %.
• alcohol components (a) other than aliphatic diols having 2 to 5 carbon atoms include alkylene oxide adducts of aromatic diols, aliphatic diols having 6 or more carbon atoms, alicyclic diols, trivalent or higher poly hydric alcohols.
• Alkylene oxide adducts of aromatic diols preferably have formula (I):
• OR and RO are oxyalkylene groups, R is each independently an ethylene or propylene group, x and y indicate the average number of added moles of alkylene oxide, each a positive number, and x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less).
• Examples of the alkylene oxide adduct of bisphenol A represented by formula (I) include a propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane and ethylene oxide of 2,2-bis(4-hydroxyphenyl)propane. adducts and the like. You may use these 1 type(s) or 2 or more types.
• Aliphatic diols having 6 or more carbon atoms include, for example, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, 12-dodecanediol and 1,4-butenediol.
• alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxide adducts having 2 to 4 carbon atoms of hydrogenated bisphenol A (average number of moles added: 2 above and below 12).
• trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol. One or more of these alcohol components may be used.
• the carboxylic acid component (b) examples include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and trivalent or higher carboxylic acid compounds.
• the carboxylic acid component (b) preferably contains an aromatic dicarboxylic acid compound from the viewpoint of suppressing surface exposure of the resin (C).
• aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, and terephthalic acid. Among these, at least one selected from terephthalic acid and isophthalic acid is more preferable from the above viewpoint.
• the content of the aromatic dicarboxylic acid compound in the carboxylic acid component (b) is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol%, from the viewpoint of suppressing the surface exposure of the resin (C). mol % or more, and preferably 100 mol % or less.
• aliphatic dicarboxylic acid compound examples include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and may be substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
• Aliphatic dicarboxylic acids such as succinic acid and adipic acid are included.
• succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include octyl succinic acid and dodecenyl succinic acid (tetrapropenyl succinic acid). Among these, fumaric acid is preferred.
• the content of the aliphatic dicarboxylic acid compound in the carboxylic acid component (b) is preferably 40 mol % or less, more preferably 30 mol % or less, still more preferably 20 mol % from the viewpoint of obtaining a toner excellent in low-temperature fixability. or less, preferably 0 mol % or more.
• trivalent or higher carboxylic acid compounds examples include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, trimellitic acid and its anhydride are preferred.
• the content of the trivalent or higher carboxylic acid compound in the carboxylic acid component (b) is preferably 60 mol % or less, more preferably 30 mol % or less, and still more preferably 10 mol % or less from the viewpoint of low-temperature fixability. Yes, 0 mol % or more.
• the alcohol component (a) may contain a monovalent alcohol
• the carboxylic acid component (b) may contain a monovalent carboxylic acid compound, as appropriate.
• the equivalent ratio of the carboxy group of the carboxylic acid component (b) to the hydroxyl group of the alcohol component (a) [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably It is 1.3 or less, more preferably 1.2 or less.
• the resin (A) may be produced, for example, by polycondensing raw material monomers containing the alcohol component (a) and the carboxylic acid component (b).
• Polycondensation of the alcohol component (a) and the carboxylic acid component (b) can be carried out, for example, in an inert gas atmosphere in the presence of an esterification catalyst, an esterification co-catalyst, a polymerization inhibitor, etc., if necessary. C. to 250.degree. C. or less.
• esterification catalyst include tin compounds such as dibutyltin oxide and di(2-ethylhexanoate)tin (II), and titanium compounds such as titanium diisopropoxybis(triethanolamine).
• Esterification cocatalysts that may be used with the esterification catalyst include, for example, gallic acid.
• the amount of the esterification catalyst used is preferably 0.01 parts by mass or more and 10 parts by mass with respect to the total amount of 100 parts by mass of the alcohol component (a) and the carboxylic acid component (b), which are raw material monomers of the resin (A). It is below.
• the amount of the esterification co-catalyst used is preferably 0.001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass as the total of the alcohol component (a) and the carboxylic acid component (b).
• polymerization inhibitors include radical polymerization inhibitors such as 4-tert-butylcatechol.
• the amount of the polymerization inhibitor used is preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the total amount of the alcohol component (a) and the carboxylic acid component (b). .
• the softening point of the resin (A) is preferably 70° C. or higher, more preferably 80° C. or higher, and still more preferably 90° C. or higher from the viewpoint of heat-resistant storage stability, and preferably 130° C. or higher from the viewpoint of low-temperature fixability. °C or less, more preferably 120°C or less, and still more preferably 110°C or less.
• the glass transition temperature of the resin (A) is preferably 30° C. or higher, more preferably 40° C. or higher, and still more preferably 45° C. or higher from the viewpoint of heat-resistant storage stability. It is 80° C. or lower, more preferably 70° C. or lower, and still more preferably 60° C. or lower.
• the acid value of resin (A) is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less. and more preferably 25 mgKOH/g or less.
• the softening point, glass transition temperature, and acid value of the resin (A) can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time, and cooling rate. is determined by the method described in Examples. When two or more resins (A) are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the ranges described above.
• the amorphous resin preferably contains 90% by mass or more of the amorphous polyester resin (A).
• the content of the resin (A) in the amorphous resin is more preferably 92% by mass or more, still more preferably 95% by mass or more, and still more preferably 97% by mass. or more, and not more than 100% by mass, preferably 100% by mass.
• the amorphous resin may contain a resin in addition to the resin (A) within a range that does not impair the effects of the present application.
• a resin examples include an amorphous polyester resin (B) (hereinafter simply referred to as "resin (B)") that does not contain an aliphatic diol whose alcohol component has 2 to 5 carbon atoms, and other polyester resins. are mentioned.
• the resin (B) examples include polyester resins and modified polyester resins. Modified polyester resins include, for example, urethane-modified polyester resins, epoxy-modified polyester resins, and composite resins containing polyester resin segments and addition polymerized resin segments. Among these, polyester resins and composite resins containing polyester resin segments and addition polymerized resin segments are preferred.
• Examples of the alcohol component of the resin (B) include alkylene oxide adducts of aromatic diols, aliphatic diols, alicyclic diols, and polyhydric alcohols having a valence of 3 or more.
• the alkylene oxide adduct of aromatic diol is exemplified by the alkylene oxide adduct of bisphenol A represented by formula (I) in resin (A) described above, and the preferred range is also the same.
• the content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, More preferably, it is 100 mol %.
• aliphatic diols examples include aliphatic diols excluding aliphatic diols having 2 to 5 carbon atoms.
• the alicyclic diol and the polyhydric alcohol having a valence of 3 or more are exemplified by the alicyclic diol and the polyhydric alcohol having a valence of 3 or more in the resin (A) described above, and the preferred range is also the same.
• Examples of the carboxylic acid component of the resin (B) include the carboxylic acid components exemplified for the resin (A) described above. Specifically, aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, trivalent or higher A carboxylic acid compound may be mentioned.
• the amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol % or less, more preferably 75 mol % or less.
• the amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, and preferably 80 mol% or less, more preferably It is 70 mol % or less, more preferably 60 mol % or less.
• the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% in the carboxylic acid component. and preferably 30 mol % or less, more preferably 20 mol % or less, still more preferably 15 mol % or less.
• carboxylic acid components may be used.
• the equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.
• the resin (B) is a composite resin
• the same composite resin as the composite resin (D) described later can be used as the composite resin.
• the resin (B) is a polyester resin
• the resin (B) can be prepared by the same method as the method for producing the polyester resin (A), and the reaction conditions and the like are also the same.
• the resin (B) is a composite resin containing a polyester resin segment and an addition polymerized resin segment
• the resin (B) may be produced, for example, by a method similar to the method for producing the composite resin (D) described below. .
• the softening point of the resin (B) is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 95° C. or higher. It is preferably 140° C. or lower, more preferably 125° C. or lower.
• the glass transition temperature of the resin (B) is preferably 30° C. or higher, more preferably 35° C. or higher, and still more preferably 40° C. or higher. It is more preferably 70° C. or lower, still more preferably 65° C. or lower.
• the acid value of the resin (B) is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less. and more preferably 30 mgKOH/g or less.
• the softening point, glass transition temperature, and acid value of the resin (B) can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time, and cooling rate. The value is determined by the method described in Examples. When two or more resins (B) are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the ranges described above.
• the crystalline resin is used as a binder resin for toner and contains a crystalline polyester resin (C) which is a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d). Since the resin (C) has a structure derived from the alcohol component (c) containing ethylene glycol, its hydrophilicity is relatively improved. Therefore, in the production method of the present invention, it is considered possible to exist in the vicinity of the surface of the aggregated particles 1 during emulsification aggregation.
• a crystalline polyester resin (C) which is a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d). Since the resin (C) has a structure derived from the alcohol component (c) containing ethylene glycol, its hydrophilicity is relatively improved. Therefore, in the production method of the present invention, it is considered possible to exist in the vicinity of the surface of the aggregated particles 1 during emulsification aggregation.
• Resin (C) is a polycondensate of alcohol component (c) and carboxylic acid component (d).
• Alcohol component (c) includes ethylene glycol.
• Alcohol component (c) may contain ⁇ , ⁇ -aliphatic diols in addition to ethylene glycol.
• ⁇ , ⁇ -aliphatic diols examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol.
• the content of ethylene glycol in the alcohol component (c) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, from the viewpoint of improving the hydrophilicity of the resin (C). It is more preferably 95 mol % or more and 100 mol % or less, still more preferably 100 mol %.
• the alcohol component (c) may contain other alcohol components different from the ⁇ , ⁇ -aliphatic diol.
• Other alcohol components include, for example, aliphatic diols other than ⁇ , ⁇ -aliphatic diols, aromatic diols, trihydric or higher alcohols, and the like. One or more of these alcohol components may be used.
• Carboxylic acid component (d) preferably comprises an aliphatic dicarboxylic acid.
• the number of carbon atoms in the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 4 or more, from the viewpoint of improving the hydrophilicity of the resin (C) and the balance between the hydrophilicity of the resin (C) and the hydrophilicity of the resin (A). is 8 or more, more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
• Examples of aliphatic dicarboxylic acids include fumaric acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like.
• linear saturated aliphatic dicarboxylic acids are preferred, sebacic acid, dodecanedioic acid and tetradecanedioic acid are preferred, and sebacic acid is more preferred.
• sebacic acid is more preferred.
• One or more of these carboxylic acid components may be used.
• the amount of the aliphatic dicarboxylic acid is preferably 80 in the carboxylic acid component. It is mol % or more, more preferably 85 mol % or more, still more preferably 90 mol % or more, still more preferably 95 mol % or more, and 100 mol % or less, still more preferably 100 mol %.
• the carboxylic acid component may contain other carboxylic acid components different from the aliphatic dicarboxylic acid.
• Other carboxylic acid components include, for example, monovalent carboxylic acids such as stearic acid; aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids.
• monovalent carboxylic acids such as stearic acid
• aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid
• trivalent or higher polyvalent carboxylic acids may be used.
• the equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.
• the softening point of the resin (C) is preferably 60° C. or higher, more preferably 65° C. or higher, still more preferably 70° C. or higher, and preferably 150° C. or lower, more preferably 120° C., from the viewpoint of heat-resistant storage stability. °C or less, more preferably 110°C or less.
• the melting point of the resin (C) is preferably 50°C or higher, more preferably 55°C or higher, still more preferably 60°C or higher, and preferably 140°C or lower, more preferably 110°C, from the viewpoint of heat resistance and storage stability. 100° C. or less, more preferably 100° C. or less.
• the acid value of resin (C) is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and is preferably 25 mgKOH/g or less, more preferably 20 mgKOH/g or less, still more preferably 15 mgKOH/g or less. is.
• the softening point, melting point, and acid value of the resin (C) can be appropriately adjusted according to the type and ratio of raw material monomers, and manufacturing conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples below. When two or more resins (C) are used in combination, the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the ranges described above.
• the resin (C) is obtained, for example, by polycondensation of the alcohol component (c) and the carboxylic acid component (d).
• the conditions for polycondensation for example, the conditions shown in the polycondensation for resin (A) described above can be applied.
• the crystalline resin preferably contains 90% by mass or more of the crystalline polyester resin (C).
• the content of the resin (C) in the crystalline resin is more preferably 92% by mass or more, still more preferably 95% by mass or more, still more preferably 97% by mass or more, from the viewpoint of obtaining a toner excellent in low-temperature fixability. , and not more than 100% by mass, preferably 100% by mass.
• the total content of the resin (A) and the resin (C) in the amorphous resin and the crystalline resin in the resin particles is preferably 80 from the viewpoint of obtaining a toner having excellent low-temperature fixability and a narrow charge amount distribution. % by mass or more, more preferably 90% by mass or more, and 100% by mass or less, preferably 100% by mass.
• the mass ratio of the resin (C) to the resin (A) [resin (C)/resin (A)] is preferably 5/95 or more from the viewpoint of obtaining a toner having excellent low-temperature fixability and a narrow charge amount distribution. , more preferably 10/90 or more, more preferably 15/85 or more, and preferably 40/60 or less, more preferably 30/70 or less, still more preferably 25/75 or less.
• the resin particles of the amorphous resin and the resin particles of the crystalline resin may be produced as an aqueous dispersion of resin particles containing the amorphous resin and the crystalline resin in the same or different particles.
• the aqueous medium used for the aqueous dispersion one containing water as a main component is preferable.
• Dispersion can be carried out using a known method, but it is preferable to disperse by a phase inversion emulsification method.
• the phase inversion emulsification method include a method of phase inversion emulsification by adding an aqueous medium to an organic solvent solution of an amorphous resin and/or a crystalline resin or a molten amorphous resin and/or a crystalline resin. be done.
• a method of phase inversion emulsification by adding an aqueous medium to a solution of the resin in an organic solvent is preferred.
• an aqueous dispersion of resin particles containing the amorphous resin and the crystalline resin in the same particles is produced.
• the organic solvent used for the phase inversion emulsification is not particularly limited as long as it dissolves the amorphous resin and the crystalline resin and is water-soluble. Examples thereof include methyl ethyl ketone.
• a neutralizing agent may be added to the organic solvent solution. Neutralizing agents include, for example, basic substances.
• Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine. Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferable.
• the degree of neutralization of the amorphous resin and/or crystalline resin contained in the resin particles is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol%. and preferably 100 mol % or less, more preferably 80 mol % or less, still more preferably 70 mol % or less.
• the degree of neutralization of the amorphous resin and/or the crystalline resin contained in the resin particles can be determined by the following formula.
• Degree of neutralization (mol%) [ ⁇ neutralizing agent added mass (g)/neutralizing agent equivalent ⁇ /[ ⁇ weighted average acid value of resin constituting resin particles (mgKOH/g) ⁇ constituting resin particles Mass of resin (g) ⁇ / (56 ⁇ 1000)]]] ⁇ 100
• the temperature of the organic solvent solution when adding the aqueous medium is preferably at least the glass transition temperature of the resin (A). It is more preferably 60° C. or higher, still more preferably 65° C. or higher, still more preferably 70° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower, still more preferably 80° C. or lower.
• the organic solvent may be removed from the resulting dispersion by distillation or the like.
• the resin particles may be isolated by filtration or the like.
• the residual amount of the organic solvent in the dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably substantially 0% by mass.
• the volume-median particle size D50 of the resin particles in the dispersion is preferably 0.05 ⁇ m or more, more preferably 0.08 ⁇ m or more, from the viewpoint of obtaining a toner with excellent low-temperature fixability and a narrow charge amount distribution. Yes, and preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.3 ⁇ m or less.
• the CV value of the resin particles in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40%, from the viewpoint of obtaining a toner having excellent low-temperature fixability and a narrow charge distribution. % or less, more preferably 35% or less.
• the solid content concentration of the aqueous dispersion of resin particles is preferably 5% by mass or more, more preferably 10% by mass, from the viewpoint of improving productivity of the toner and improving the dispersion stability of the aqueous dispersion of resin particles. % or more, more preferably 15 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less, still more preferably 25 mass % or less.
• solid content is the total amount of a non-volatile component.
• the agglomerated particles 1 may contain a colorant and/or a release agent. Additives such as reinforcing fillers such as substances, antioxidants, anti-aging agents, and cleaning improvers may also be included.
• the aqueous medium is a medium containing water as a main component, and the content of water in the aqueous medium is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass. or more and 100% by mass or less.
• water deionized water, ion-exchanged water, or distilled water is preferred.
• Components other than water that can constitute an aqueous medium together with water include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran dissolved in water. organic solvent is used. Among these, alkyl alcohols having 1 to 5 carbon atoms are preferred, and ethanol is more preferred.
• the colorant is preferably contained in the aggregated particles 1 by mixing the colorant with the resin particles as a dispersion liquid of the colorant particles and causing them to aggregate.
• the colorant all dyes, pigments, etc. used as colorants for toners can be used. Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, disazo yellow, and the like. are mentioned.
• the toner may be black toner or color toner other than black.
• the colorant particles are preferably contained in the aggregated particles 1 by mixing and aggregating the colorant particles with the resin particles as a dispersion liquid of the colorant particles. It is preferably obtained by dispersing using a disperser. From the viewpoint of improving the dispersion stability of the colorant, the dispersion is carried out in the presence of an addition polymer (hereinafter, the addition polymer used for dispersing the colorant is also referred to as "addition polymer E”) or a surfactant. It is preferable to use Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants.
• the addition polymer E preferably has structural units derived from the addition polymerizable monomer a having an aromatic group, and further includes an addition polymerizable monomer b having an ionic group and an addition polymerizable monomer c having a polyalkylene oxide group. , and macromonomer d.
• addition polymer E described in JP-A-2021-026129.
• the releasing agent is preferably contained in the aggregated particles 1 by mixing the release agent-containing release agent particle dispersion liquid with the resin particles and causing them to aggregate.
• Release agents include, for example, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; and oxides thereof; carnauba wax. , montan waxes or their deacidified waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may use 1 type(s) or 2 or more types.
• the melting point of the release agent is preferably 60° C. or higher, more preferably 70° C. or higher, and is preferably 160° C. or lower, more preferably 140° C. or lower, still more preferably 120° C. or lower, and still more preferably 100° C. or lower. is.
• the content of the release agent in the toner particles is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably is 15% by mass or less, more preferably 10% by mass or less.
• the release agent particle dispersion can be obtained using a surfactant, but is preferably obtained by mixing the release agent and resin particles S described later.
• the release agent particles are stabilized by the resin particles S, and the release agent can be dispersed in an aqueous medium without using a surfactant. Dispersion becomes possible. It is considered that the release agent particle dispersion liquid has a structure in which a large number of resin particles S adhere to the surface of the release agent particles.
• the resin constituting the resin particles S in which the release agent is dispersed is preferably a polyester-based resin, and more preferably a composite resin (D) having a polyester resin segment and an addition polymerized resin segment.
• the composite resin (D) is a modified polyester resin, and examples thereof include composite resins containing polyester resin segments and addition polymerized resin segments.
• Examples of the alcohol component of the composite resin (D) include alkylene oxide adducts of aromatic diols, aliphatic diols, alicyclic diols, and polyhydric alcohols having a valence of 3 or more.
• the alkylene oxide adduct of aromatic diol is exemplified by the alkylene oxide adduct of bisphenol A represented by formula (I) in resin (A) described above, and the preferred range is also the same.
• the content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, More preferably, it is 100 mol %.
• aliphatic diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol.
• the alicyclic diol and the polyhydric alcohol having a valence of 3 or more are exemplified by the alicyclic diol and the polyhydric alcohol having a valence of 3 or more in the resin (A) described above, and the preferred range is also the same.
• Examples of the carboxylic acid component of the composite resin (D) include the carboxylic acid components exemplified for the resin (A) described above. Specifically, aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, trivalent or higher carboxylic acid compounds of. Among them, terephthalic acid and succinic acid are preferred.
• the amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol % or less, more preferably 75 mol % or less.
• the amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, and preferably 80 mol% or less, more preferably It is 70 mol % or less, more preferably 60 mol % or less.
• the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% in the carboxylic acid component. and preferably 30 mol % or less, more preferably 20 mol % or less, still more preferably 15 mol % or less.
• carboxylic acid components may be used.
• the equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.
• addition-polymerized resin segment of the composite resin (D) examples include addition-polymerized products of raw material monomers containing styrene compounds.
• Styrenic compounds include, for example, unsubstituted or substituted styrene.
• substituents for styrene include alkyl groups having 1 to 5 carbon atoms, halogen atoms, alkoxy groups having 1 to 5 carbon atoms, sulfonic acid groups, and salts thereof.
• Styrenic compounds include, for example, styrene, methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Among these, styrene is preferred.
• the content of the styrenic compound in the raw material monomers of the addition polymerized resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 75% by mass or more, and 100% by mass or less. , preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.
• Raw material monomers other than styrenic compounds include, for example, (meth)acrylates such as alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; ethylene, propylene, butadiene, etc. olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; .
• (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates are more preferred.
• the number of carbon atoms in the alkyl group in the alkyl (meth)acrylate is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, and is preferably 24 or less, more preferably 22 or less, and still more preferably 20. It is below.
• alkyl (meth) acrylates examples include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, (meth) ) (iso)amyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (meth)acrylic acid ( iso) dodecyl, (iso) palmityl (meth) acrylate, (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate and the like, preferably 2-ethylhexyl (meth) acrylate or ( Stearyl meth)acrylate, more preferably stearyl (me
• the (meth)acrylic acid ester content in the raw material monomers of the addition polymerized resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or more. % by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less.
• the total amount of the styrenic compound and the (meth)acrylic acid ester in the raw material monomers of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably. is 100% by mass.
• the composite resin (D) preferably has structural units derived from bi-reactive monomers that are covalently bonded to the polyester resin segment and the addition polymerized resin segment.
• the “structural unit derived from a bireactive monomer” means a unit obtained by reacting a functional group and an addition polymerizable group of a bireactive monomer. Examples of addition polymerizable groups include carbon-carbon unsaturated bonds (ethylenically unsaturated bonds).
• the bi-reactive monomers include, for example, addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule. .
• addition polymerizable monomers having at least one functional group selected from hydroxyl groups and carboxy groups are preferred, and addition polymerizable monomers having a carboxy group are more preferred.
• Addition-polymerizable monomers having a carboxy group include, for example, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred, from the viewpoint of reactivity in both polycondensation reaction and addition polymerization reaction.
• the amount of structural units derived from the bireactive monomer is preferably It is 1 mol part or more, more preferably 5 mol parts or more, still more preferably 8 mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.
• the content of the polyester resin segment in the composite resin (D) is preferably 35% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less, and more It is preferably 85% by mass or less, more preferably 75% by mass or less.
• the content of the addition polymerized resin segment in the composite resin (D) is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 60% by mass or less, It is more preferably 55% by mass or less, still more preferably 45% by mass or less.
• the amount of structural units derived from the bi-reactive monomer in the composite resin (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more,
• the content is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less.
• the total amount of the polyester resin segment, the addition polymerization resin segment, and the structural units derived from the bireactive monomer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass. or more, and 100% by mass or less, more preferably 100% by mass.
• the above amounts are calculated based on the ratio of the amounts of the polyester resin segment, raw material monomers for the addition polymerization resin segment, bi-reactive monomer, and radical polymerization initiator. Based on mass excluding mass. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment in the calculation.
• the composite resin (D) is a composite resin containing a polyester resin segment and an addition polymerized resin segment, for example, a step A of polycondensing an alcohol component and a carboxylic acid component, and a raw material monomer of the addition polymerized resin segment and both reactive You may manufacture by the method containing the process B which carries out addition polymerization of a monomer.
• Process B may be performed after process A, process A may be performed after process B, or process A and process B may be performed simultaneously.
• step A a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is performed, then the remainder of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of step A and the both reactive monomers or both A method of further advancing the polycondensation reaction with the carboxy group of the constituent site derived from the reactive monomer is preferred.
• step A polycondensation may be carried out using the esterification catalyst and the esterification co-catalyst described in the method for producing the polyester resin (A) in the same amounts. Further, when using a monomer having an unsaturated bond such as fumaric acid for polycondensation, if necessary, the polymerization inhibitor described in the method for producing the polyester resin (A) is used in the same amount.
• the temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.
• radical polymerization initiator for addition polymerization in step B examples include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and 2,2′-azobis(2,4-dimethylvaleronitrile) such as azo compounds.
• the amount of the radical polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer for the addition polymerization resin segment.
• the addition polymerization temperature is preferably 110° C. or higher, more preferably 130° C. or higher, and preferably 230° C. or lower, more preferably 220° C. or lower, and still more preferably 210° C. or lower.
• the softening point of the composite resin (D) is preferably 70° C. or higher, more preferably 80° C. or higher, still more preferably 85° C. or higher, and preferably 140° C. or lower, more preferably 120° C. or lower, still more preferably 100° C. or less.
• the glass transition temperature of the composite resin (D) is preferably 30° C. or higher, more preferably 35° C. or higher, and still more preferably 40° C. or higher, and is preferably 80° C. or lower from the viewpoint of further improving low-temperature fixability. , more preferably 70° C. or lower, still more preferably 60° C. or lower.
• the acid value of the composite resin (D) is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and still more preferably 15 mgKOH from the viewpoint of obtaining fine resin particles and obtaining a fine release agent particle dispersion. /g or more, more preferably 20 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less.
• the softening point, glass transition temperature, and acid value of the composite resin (D) can be appropriately adjusted depending on the type and amount of raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples. When two or more composite resins (D) are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the ranges described above.
• a dispersion of the resin particles S can be obtained, for example, by the above-described phase inversion emulsification method.
• the volume-median particle size D50 of the resin particles S is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and preferably 3.0 ⁇ m or less, from the viewpoint of the dispersion stability of the release agent particles. , and more preferably 1.0 ⁇ m or less.
• the CV value of the resin particles S is preferably 10% or more, more preferably 15% or more, and preferably 40% or less, more preferably 35% or less. More preferably, it is 30% or less.
• the volume-median particle diameter D50 and CV value of the resin particles S are measured by the methods described in Examples.
• the releasing agent particle dispersion is obtained, for example, by dispersing the releasing agent, the dispersion of the resin particles S, and, if necessary, an aqueous medium at a temperature equal to or higher than the melting point of the releasing agent using a homogenizer, a high-pressure disperser, or an ultrasonic disperser. obtained by dispersing using a dispersing machine such as
• the heating temperature during dispersion is preferably the melting point of the release agent or higher and 80° C. or higher, more preferably 85° C. or higher, still more preferably 90° C. or higher, and preferably softens the resin contained in the resin particles S. 10° C. higher than the point and 100° C. or less, more preferably 98° C. or less, still more preferably 95° C. or less.
• the amount of the resin particles S is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and preferably 100 parts by mass or less with respect to 100 parts by mass of the release agent. , more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.
• the volume-median particle size D50 of the release agent particles is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and still more preferably 0.2 ⁇ m or more, from the viewpoint of obtaining uniform aggregated particles 1 by aggregation. , and preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and even more preferably 0.6 ⁇ m or less.
• the CV value of the release agent particles is preferably 10% or more, more preferably 15% or more, and preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
• the volume-median particle diameter D50 and CV value of the release agent particles are measured by the methods described in Examples.
• the aggregated particles 1 may also contain additives such as charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleaning improvers. may contain.
• additives such as charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleaning improvers. may contain.
• the dispersion of each particle is mixed to prepare a mixed dispersion, from the viewpoint of improving the dispersion stability of the resin particles, release agent particles, colorant particles, etc. may be performed in the presence of
• surfactants include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
• the total amount used is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and still more preferably 0.1 part by mass or more, with respect to 100 parts by mass of the total amount of the resin particles. It is 5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.
• flocculant In the step of aggregating the resin particles, it is preferable to add an aggregating agent from the viewpoint of efficient aggregation.
• flocculants include cationic surfactants such as quaternary salts, organic flocculants such as polyethyleneimine, and inorganic flocculants.
• inorganic flocculants include inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium nitrate; and divalent or higher metal complexes. .
• a monovalent to pentavalent inorganic flocculant is preferable, and a monovalent to divalent inorganic metal salt and inorganic ammonium salt are more preferable, and an inorganic ammonium salt. is more preferred, and ammonium sulfate is even more preferred.
• a flocculant for example, 5 parts by mass or more and 50 parts by mass per 100 parts by mass of the resin in the resin particles is added to a mixed dispersion containing resin particles, release agent particles, and colorant particles at 0 ° C. or higher and 40 ° C. or lower. Part or less of a flocculant is added, and the resin particles, release agent particles, and colorant particles are flocculated in an aqueous medium to obtain flocculated particles 1 . Furthermore, from the viewpoint of promoting aggregation, it is preferable to raise the temperature of the dispersion after adding the aggregating agent.
• Methods for stopping aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation terminator is preferred.
• aggregation terminating agent As the aggregation terminator, a surfactant is preferred, and an anionic surfactant is more preferred.
• anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates, and the like. These may be used alone or in combination of two or more.
• the aggregation terminator may be added in the form of an aqueous solution.
• the addition amount of the aggregation terminator is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the resin in the resin particles, from the viewpoint of reliably preventing unnecessary aggregation, and , preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of reducing the residual amount in the toner.
• the volume-median particle diameter D50 of the aggregated particles 1 is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 4 ⁇ m or more, and is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, further preferably 7 ⁇ m or less. is.
• the agglomerated particles 1 obtained contain an amorphous resin (preferably an amorphous polyester-based resin). may be provided to obtain aggregated particles 2 by aggregating the shell resin particles.
• an amorphous resin preferably an amorphous polyester-based resin
• toner particles having a core-shell structure can be obtained.
• the above-described polyester resin (B) is exemplified as the amorphous resin used for the resin particles for the shell.
• the resin particles for the shell are obtained by the same method as for the resin particles containing the amorphous resin and/or the crystalline resin described above.
• the toner production method includes a step of aggregating the shell resin particles
• a method of stopping aggregation by adding an aggregation terminator is preferred.
• the aggregated particles are fused in an aqueous medium. By fusion, each particle contained in the aggregated particles is fused to obtain fused particles.
• a resin having the highest glass transition temperature among the resins contained in the aggregated particles is used from the viewpoint of improving the fusibility of the aggregated particles and achieving both low-temperature fixability and heat-resistant storage stability of the toner. is maintained at a temperature equal to or higher than the glass transition temperature of The holding temperature for fusing the aggregated particles is preferably at least 5° C.
• the time for holding at a temperature equal to or higher than the glass transition temperature of the resin is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably 30 minutes, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. and preferably 240 minutes or less, more preferably 180 minutes or less, even more preferably 120 minutes or less, and even more preferably 90 minutes or less.
• the volume-median particle diameter D50 of the fused particles obtained by fusion is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 4 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less. , and more preferably 7 ⁇ m or less.
• the degree of circularity of the fused particles obtained by fusion bonding is preferably 0.955 or more, more preferably 0.960 or more, and is preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less. It is preferable that the fusion-bonding is completed after reaching the above-mentioned preferable degree of circularity. Circularity is measured by the method described in Examples.
• a post-treatment step may be performed after the fusing step to obtain toner particles by isolating the fusing particles. Since the fused particles obtained in the fused step are present in the aqueous medium, it is preferable to perform solid-liquid separation first. A suction filtration method or the like is preferably used for the solid-liquid separation. Washing is preferably performed after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, it is preferable to wash with an aqueous medium at a temperature not higher than the cloud point of the surfactant. Washing is preferably performed multiple times. Drying is then preferably carried out. The drying method includes, for example, a vacuum low temperature drying method, a vibrating fluidized bed drying method, a spray drying method, a freeze drying method, and a flash jet method.
• the volume-median particle diameter D50 of the toner particles is preferably 2 ⁇ m or more, more preferably 3 ⁇ m, from the viewpoints of obtaining a toner with excellent low-temperature fixability and a narrow charge amount distribution, and from the viewpoint of further improving the cleaning property of the toner. Above all, it is more preferably 4 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 7 ⁇ m or less.
• the circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, from the viewpoint of obtaining high-quality images, and is preferably 0.990 or less, more preferably from the viewpoint of cleanability. is 0.985 or less, more preferably 0.980 or less.
• the CV value of the toner particles is preferably 10% or more, more preferably 15% or more, and still more preferably 20% or more from the viewpoint of improving toner productivity. It is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
• the volume-median particle size D50 of the toner particles can be measured by the method described in the Examples.
• the electrostatic charge image developing toner of the present invention contains toner particles.
• the toner particles can be used as the toner as it is, it is preferable to use the toner after adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
• Examples of the external additive include fine particles of inorganic materials such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and fine particles of polymers such as polycarbonate, polymethyl methacrylate, and silicone resin.
• hydrophobic silica is preferred.
• One type of external additive may be used alone, or two or more types may be used.
• two or more types of hydrophobic silica having different particle sizes may be used.
• the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and even more preferably 4 parts by mass or less.
• Toners are used for electrostatic image development in electrophotographic printing.
• the toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.
• the present invention further discloses the following embodiments.
• a method for producing a toner for electrostatic charge image development comprising the steps of aggregating and fusing resin particles containing an amorphous resin and a crystalline resin in the same or different particles in an aqueous medium
• the amorphous resin contains an amorphous polyester resin (A) which is a polycondensate of an alcohol component (a) containing an aliphatic diol having 2 to 5 carbon atoms and a carboxylic acid component (b),
• the crystalline resin contains a crystalline polyester resin (C) which is a polycondensate of an alcohol component (c) containing ethylene glycol and a carboxylic acid component (d).
• the aliphatic diol having 2 to 5 carbon atoms is preferably ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl- 1,3-propanediol and neopentyl glycol, more preferably ethylene glycol, 1,2-propanediol, 2,3-butanediol and neopentyl glycol, for electrostatic charge image development according to ⁇ 1>. Toner manufacturing method.
• the content of the aliphatic diol having 2 to 5 carbon atoms in the alcohol component (a) is preferably 85 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and , 100 mol % or less, preferably 100 mol %.
• the carboxylic acid component (b) preferably contains an aromatic dicarboxylic acid compound, and more preferably contains at least one selected from terephthalic acid and isophthalic acid.
• the content of the aromatic dicarboxylic acid compound in the carboxylic acid component (b) is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and preferably 100
• the softening point of the amorphous polyester resin (A) is preferably 70° C. or higher, more preferably 80° C. or higher, still more preferably 90° C.
• the glass transition temperature of the amorphous polyester resin (A) is preferably 30°C or higher, more preferably 40°C or higher, still more preferably 45°C or higher, and preferably 80°C or lower, more preferably 70°C.
• the acid value of the amorphous polyester resin (A) is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably is 30 mgKOH/g or less, more preferably 25 mgKOH/g or less.
• the content of ethylene glycol in the alcohol component (c) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and
• the carboxylic acid component (d) preferably contains an aliphatic dicarboxylic acid, and the number of carbon atoms in the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably
• the carboxylic acid component (d) preferably contains a linear saturated aliphatic dicarboxylic acid, more preferably at least one selected from sebacic acid, dodecanedioic acid, and tetradecanedioic acid, and still more preferably sebacic acid. and ⁇ 11>.
• the amount of the aliphatic dicarboxylic acid in the carboxylic acid component (d) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more,
• the softening point of the crystalline polyester resin (C) is preferably 60° C. or higher, more preferably 65° C. or higher, still more preferably 70° C. or higher, and preferably 150° C. or lower, more preferably 120° C. or lower, The method for producing a toner for developing an electrostatic charge image according to any one of ⁇ 1> to ⁇ 14>, wherein the temperature is more preferably 110° C. or lower.
• the melting point of the crystalline polyester resin (C) is preferably 50° C. or higher, more preferably 55° C. or higher, still more preferably 60° C. or higher, and preferably 140° C. or lower, more preferably 110° C. or lower.
• the acid value of the crystalline polyester resin (C) is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and is preferably 25 mgKOH/g or less, more preferably 20 mgKOH/g or less, and still more preferably
• the mass ratio of the crystalline polyester resin (C) to the amorphous polyester resin (A) [crystalline polyester resin (C)/amorphous polyester resin (A)] is preferably 5/95 or more, more preferably 10/90 or more, more preferably 15/85 or more, and preferably 40/60 or less, more preferably 30/70 or less, still more preferably 25/75 or less, ⁇ 1> to ⁇ 17>
• a resin particle dispersion containing the resin particles In the aggregating step, a resin particle dispersion containing the resin particles, a colorant particle dispersion containing the colorant particles containing the colorant, and/or a release agent containing the release agent particles containing the release agent.
• the method for producing a toner for developing an electrostatic charge image according to ⁇ 19> comprising mixing with a template particle dispersion to aggregate the particles.
• the electrostatic charge image developing device according to ⁇ 21>, wherein the resin constituting the resin particles S is preferably a polyester-based resin, more preferably a composite resin (D) having a polyester resin segment and an addition polymerized resin segment. Toner manufacturing method.
• volume median particle size D50 of the aggregated particles was measured as follows. ⁇ Measuring machine: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.) ⁇ Aperture diameter: 50 ⁇ m ⁇ Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.) ⁇ Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.) Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured again, and the particle size The volume median particle size D50 was determined from the distribution.
• volume Median Particle Diameter D50 and CV Value of Toner Particles The volume median particle size D50 of the toner particles was measured as follows. The measuring device, aperture diameter, analysis software, and electrolytic solution used were the same as those used in the measurement of the volume-median particle diameter D50 of the aggregated particles described above.
• Production Examples A2 and A4 (Production of resins A-2 and A-4) Resins A-2 and A-4 were obtained in the same manner as in Production Example A1, except that the starting monomers for the polyester resin were changed as shown in Table 1. Table 1 shows physical properties.
• Production Example A3 (Production of Resin A-3) A 10 L volume equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractionation tube through which hot water at 98 ° C. was passed, a stirrer and a thermocouple was added. was placed in a four-necked flask. In a nitrogen atmosphere, the reaction system was kept at 180° C. for 1 hour, then heated from 180° C. to 230° C. at a rate of 10° C./h, and then held at 230° C. for 5 hours for polycondensation.
• Production Example A5 (Production of Resin A-5) A polyester resin raw material monomer other than isophthalic acid, an esterification catalyst, and an esterification co-catalyst shown in Table 1 were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple. In a nitrogen atmosphere, the reaction system was kept at 205° C. for 1 hour, then heated from 205° C. to 235° C. at a rate of 10° C./h, and then held at 235° C. for 5 hours for polycondensation.
• Production Examples C2 to C6 (Production of resins C-2 to C-6) Resins C-2 to C-6 were obtained in the same manner as in Production Example C1, except that the starting monomers for the polyester resin were changed as shown in Table 2. Table 2 shows physical properties.
• the internal pressure was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160°C, and a mixture of 2,756 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was reacted over 1 hour while maintaining the temperature at 160°C. Dropped into the system. Thereafter, the reaction system was held at 160° C. for 30 minutes, then heated to 200° C., the pressure in the flask was further lowered, and the pressure was held at 8 kPa for 1 hour.
• Production Example S1 (Production of Resin Particle Dispersion S-1) 200 g of Resin D-1 and 200 g of methyl ethyl ketone were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and dissolved at 73° C. for 2 hours. A 5 mass % sodium hydroxide aqueous solution was added to the obtained solution so that the degree of neutralization was 60 mol % with respect to the acid value of Resin D-1, and the mixture was stirred for 30 minutes. Then, while maintaining the temperature at 73° C. and stirring at 280 r/min, 700 g of deionized water was added over 50 minutes for phase inversion emulsification.
• the obtained solution was kept at 73° C., and methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30° C. while stirring at 280 r/min, and then deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining a resin particle dispersion S-1. .
• Table 5 shows physical properties.
• Production Example W1 (Production of Release Agent Particle Dispersion W-1) 120 g of deionized water, 86 g of resin particle dispersion S-1, and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiro Co., Ltd., melting point 75° C.) were added to a 1 L beaker, and the mixture was heated to 90 to 95° C. The mixture was melted while maintaining the temperature at 20° C. and stirred to obtain a molten mixture.
• HNP-9 paraffin wax
• Production Example W2 (Production of Release Agent Particle Dispersion W-2) Release agent particle dispersion was prepared in the same manner as in Production Example W1, except that the type of release agent was changed to Fischer-Tropsch wax "FNP-0090" (manufactured by Nippon Seiro Co., Ltd., melting point 90 ° C.) shown in Table 6. W-2 was obtained. Table 6 shows the physical properties of the release agent particles in the release agent particle dispersion W-2.
• Example 1 (Production of Toner 1) 500 g of resin particle dispersion X-1, 49 g of release agent particle dispersion W-1, and release agent particle dispersion W- were placed in a 3 L four-necked flask equipped with a dehydrator, a stirrer, and a thermocouple. 2, 63 g of colorant particle dispersion Z-1, and 3.3 g of 15% by mass sodium dodecylbenzenesulfonate aqueous solution "Neopelex G-15" (manufactured by Kao Corporation, anionic surfactant). Mixed at 25°C.
• the obtained dispersion of fused particles was cooled to 30° C., the dispersion was suction filtered to separate the solid content, washed with deionized water at 25° C., and suction filtered at 25° C. for 2 hours. Thereafter, vacuum drying was performed at 33° C. for 24 hours using a vacuum constant temperature dryer “DRV622DA” (manufactured by ADVANTEC) to obtain toner particles.
• DVR622DA vacuum constant temperature dryer
• Toner 1 100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 0.04 ⁇ m), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan Co., Ltd.
• Toner 1 was obtained by adding 1.0 part by mass of the toner (manufactured by the company, number average particle diameter: 0.012 ⁇ m) into a Henschel mixer, stirring, and passing it through a 150-mesh sieve.
• Table 8 shows physical properties of the toner particles.
• the same printer with a variable temperature fixing device was prepared, the temperature of the fixing device was set to 100° C., and the toner was fixed at a speed of 0.9 seconds per sheet of A4 paper in the vertical direction to obtain a printed matter.
• the temperature of the fixing device was increased by 5° C. to fix the toner, and a printed matter was obtained.
• a piece of mending tape "Scotch (registered trademark) Mending Tape 810" manufactured by Sumitomo 3M Co., Ltd., width 18 mm
• cut into a length of 50 mm is lightly pasted from the top margin of the printed image to the solid image.
• Fixing rate (%) (reflected image density after tape removal/reflected image density before tape application) x 100
• the minimum fixing temperature T1 was defined as the lowest temperature at which the fixing rate was 90% or higher. The lower the minimum fixing temperature, the better the low-temperature fixability.
• Examples 2 to 3, 8 and Comparative Example 2 (Production of Toners 2 to 3, 8 and Toner 10) A toner was obtained in the same manner as in Example 1, except that the resin particle dispersion was changed to the aqueous dispersion shown in Table 8.
• toners 2 to 3, 8 and toner 10 were also measured for low-temperature fixability and toner charge amount distribution.
• Table 8 shows physical property values and evaluation results of the toner.
• Example 4 (Production of Toner 4)
• the resin particle dispersion was changed to the aqueous dispersion shown in Table 8, and the temperature was raised to 87°C over 1 hour for fusion of the aggregated particles 1, and the circularity became 0.970.
• Toner 4 was obtained in the same manner as in Example 1 except that the temperature was maintained at 87° C. until the temperature was reached.
• toner 4 was also measured for low-temperature fixability and toner charge amount distribution.
• Table 8 shows physical property values and evaluation results of the toner.
• Example 5 (Production of Toner 5)
• the resin particle dispersion was changed to the aqueous dispersion shown in Table 8, and the temperature was raised to 91°C over 1 hour for fusing the aggregated particles 1, and the circularity became 0.970.
• Toner 5 was obtained in the same manner as in Example 1 except that the temperature was maintained at 91° C. until the temperature was reached.
• toner 5 was also measured for low-temperature fixability and toner charge amount distribution.
• Table 8 shows physical property values and evaluation results of the toner.
• Examples 6-7 (Production of Toners 6-7)
• the resin particle dispersion was changed to the aqueous dispersion shown in Table 8, and the temperature was raised to 77°C over 1 hour for fusion of the aggregated particles 1, and the circularity became 0.970.
• Toners 6 and 7 were obtained in the same manner as in Example 1, except that the temperature was maintained at 77° C. until the temperature was reached.
• toners 6 and 7 were also measured for low-temperature fixability and toner charge amount distribution.
• Table 8 shows physical property values and evaluation results of the toner.
• Example 1 Comparative Example 1 (Production of Toner 9)
• the resin particle dispersion was changed to the aqueous dispersion shown in Table 8, and the temperature was raised to 74° C. over 1 hour to fuse the aggregated particles 1, and the circularity became 0.970.
• Toner 9 was obtained in the same manner as in Example 1 except that the temperature was maintained at 74° C. until the temperature was reached.
• toner 9 was also measured for low-temperature fixability and toner charge amount distribution.
• Table 8 shows the physical property values and evaluation results of the toner.
• Toners 1 to 8 having excellent low-temperature fixability and narrow charge amount distribution were obtained by the manufacturing method of the present invention including the step of aggregating in a medium and the step of fusing.
• the resin (C) could not exist in the vicinity of the surface of the toner during the aggregating process and the fusing process. It is considered to have become higher.
• the hydrophilicity of the resin (A), in which the alcohol component (a) is an alkylene oxide (2.2) adduct of bisphenol A was not sufficiently hydrophilic. It is thought that the exposure of .
• an electrostatic charge image developing toner which is excellent in low-temperature fixability and has a narrow charge amount distribution.
• the electrostatic charge image developing toner produced by the production method of the present invention is excellent in low-temperature fixability and has a narrow charge amount distribution. It is particularly useful for developing latent images formed in electrostatic recording methods, electrostatic printing methods, and the like.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Developing Agents For Electrophotography (AREA)
• Polyesters Or Polycarbonates (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86999225

Family Applications (1)

Country Status (2)

Citations (2)

• 2022
  • 2022-12-28 WO PCT/JP2022/048557 patent/WO2023127947A1/ja not_active Ceased
  • 2022-12-28 JP JP2022211732A patent/JP2023098716A/ja active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events